Synthesis method of beta-iodo-N-alkoxy benzotriazole compounds

A technology of hydroxybenzotriazole and synthesis method, applied in the direction of organic chemistry, etc., to achieve the effects of simple reaction operation, mild reaction conditions, and avoiding metal residues

Active Publication Date: 2017-11-24
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, so far, the synthesis methods of such compounds are rarely reported.

Method used

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  • Synthesis method of beta-iodo-N-alkoxy benzotriazole compounds
  • Synthesis method of beta-iodo-N-alkoxy benzotriazole compounds
  • Synthesis method of beta-iodo-N-alkoxy benzotriazole compounds

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Experimental program
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Effect test

Embodiment 1

[0029]

[0030] N-hydroxybenzotriazole (40.5mg, 0.3mmol), styrene (93.6mg, 0.9mmol), elemental iodine (38.1mg, 0.15mmol) and tert-butyl hydroperoxide (77.2mg, 0.6mmol, 70% aqueous solution) into the flask, add 2ml of solvent 1,2-dichloroethane, and react at 50°C for 4 hours. After the reaction was detected by TLC, compound 1 (83.3 mg) was isolated by column chromatography (eluent: petroleum ether / ethyl acetate volume ratio 6:1), with a yield of 76%.

[0031] Product characterization: colorless liquid; 1 H NMR (500MHz, CDCl 3 )δ7.93 (d, J = 8.3Hz, 1H), 7.39–7.32 (m, 6H), 7.29 (ddd, J = 8.0, 7.5, 3.0Hz, 2H), 5.69 (t, J = 7.0Hz, 1H ),3.92(dd,J=10.8,7.1Hz,1H),3.71(dd,J=10.8,7.0Hz,1H). 13 C NMR (125MHz, CDCl 3 ) δ143.12, 135.4, 130.1, 128.8, 127.90 (d, J=5.8Hz), 127.5, 124.4, 120.0, 108.8, 91.8, 2.9. HRMS (ESI) calcd for C 14 h 16 IN 4 O (M+NH 4 + )383.0369, found 383.0366.

Embodiment 2

[0033]

[0034] N-hydroxybenzotriazole (40.5mg, 0.3mmol), styrene (156mg, 1.5mmol), elemental iodine (38.1mg, 0.15mmol) and tert-butyl hydroperoxide (77.2mg, 0.6mmol, 70 % aqueous solution) into the flask, add 2ml of solvent 1,2-dichloroethane, and react at 50°C for 4 hours. After the reaction was detected by TLC, compound 1 (83.3 mg) was isolated by column chromatography (eluent: petroleum ether / ethyl acetate volume ratio 6:1), with a yield of 76%.

[0035] Product characterization: colorless liquid; 1 H NMR (500MHz, CDCl 3)δ7.93 (d, J = 8.3Hz, 1H), 7.39–7.32 (m, 6H), 7.29 (ddd, J = 8.0, 7.5, 3.0Hz, 2H), 5.69 (t, J = 7.0Hz, 1H ),3.92(dd,J=10.8,7.1Hz,1H),3.71(dd,J=10.8,7.0Hz,1H). 13 C NMR (125MHz, CDCl 3 ) δ143.12, 135.4, 130.1, 128.8, 127.90 (d, J=5.8Hz), 127.5, 124.4, 120.0, 108.8, 91.8, 2.9. HRMS (ESI) calcd for C 14 h 16 IN 4 O (M+NH 4 + )383.0369, found 383.0366.

Embodiment 3

[0037]

[0038] N-hydroxybenzotriazole (40.5mg, 0.3mmol), styrene (41.2mg, 0.9mmol), elemental iodine (76.2mg, 0.3mmol) and tert-butyl hydroperoxide (77.2mg, 0.6mmol, 70% aqueous solution) into the flask, add 2ml of solvent 1,2-dichloroethane, and react at 50°C for 4 hours. After the reaction was detected by TLC, compound 1 (83.3 mg) was isolated by column chromatography (eluent: petroleum ether / ethyl acetate volume ratio 6:1), with a yield of 76%.

[0039] Product characterization: colorless liquid; 1 H NMR (500MHz, CDCl 3 )δ7.93 (d, J = 8.3Hz, 1H), 7.39–7.32 (m, 6H), 7.29 (ddd, J = 8.0, 7.5, 3.0Hz, 2H), 5.69 (t, J = 7.0Hz, 1H ),3.92(dd,J=10.8,7.1Hz,1H),3.71(dd,J=10.8,7.0Hz,1H). 13 C NMR (125MHz, CDCl 3 ) δ143.12, 135.4, 130.1, 128.8, 127.90 (d, J=5.8Hz), 127.5, 124.4, 120.0, 108.8, 91.8, 2.9. HRMS (ESI) calcd for C 14 h 16 IN 4 O (M+NH 4 + )383.0369, found 383.0366.

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Abstract

The invention provides a synthesis method of beta-iodo-N-alkoxy benzotriazole compounds shown as a formula (III). According to the method, N-hydroxybenzotriazole shown as a formula (I), olefin compounds shown as a formula (II), an iodine source and an oxidizing agent are mixed into a polar solvent to react for 2 to 8h at 0 to 80 DEG C; after the reaction is completed, reaction liquid is obtained; reaction liquid is subjected to post treatment to obtain the beta-iodo-N-alkoxy benzotriazole compounds. The addition mole ratio of the N-hydroxybenzotriazole shown as the formula (I) to the olefin compounds shown as the formula (II) to the iodine source to the oxidizing agent is 1:(0.5 to 5):(0.5 to 1):(1 to 5). The reaction conditions are mild; safety and environment protection are realized; the substrate applicability is high; no metal catalyst participates; the operation is simple; the application to medicine synthesis is facilitated. The formulas (I), (II) and (III) are shown in the specification.

Description

(1) Technical field [0001] The invention relates to a method for synthesizing β-iodo-N-alkoxybenzotriazole compounds, which uses N-hydroxybenzotriazole as a raw material, and olefin 1,2-difunctionalization reaction Substituted alkenes are converted into corresponding β-iodo-N-alkoxybenzotriazole compounds, and a series of β-iodo-N-alkoxybenzotriazoles are obtained under mild conditions Azole derivatives. (2) Background technology [0002] β-iodo-N-alkoxybenzotriazole compounds are very important structural units that can be transformed into many other important organic compounds. [0003] For example, the halogen iodine atom contained in its molecule can undergo cross-coupling reaction with aryl boronic acid, aryl alkyne, etc. under palladium catalysis. The N-alkoxyamine structure contained in its molecule can also be converted into corresponding alkoxyamine hydrochloride, hydroxyl and other groups in the presence of acid, alkali or oxidizing agent, so as to further transf...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D249/04
CPCC07D209/48C07D249/04C07D249/18C07D471/04
Inventor 李小青陈昆许响生
Owner ZHEJIANG UNIV OF TECH
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